CN1158229C - Process for obtaining light olefins by dehydrogenation of corresponding paraffins - Google Patents
Process for obtaining light olefins by dehydrogenation of corresponding paraffins Download PDFInfo
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- CN1158229C CN1158229C CNB981178081A CN98117808A CN1158229C CN 1158229 C CN1158229 C CN 1158229C CN B981178081 A CNB981178081 A CN B981178081A CN 98117808 A CN98117808 A CN 98117808A CN 1158229 C CN1158229 C CN 1158229C
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- C07C2521/08—Silica
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
- C07C2523/04—Alkali metals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of germanium, tin or lead
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/24—Chromium, molybdenum or tungsten
- C07C2523/26—Chromium
Abstract
A process for obtaining light olefins by the dehydrogenation of the corresponding paraffins, consisting: a)in reacting in a reactor, operating at a temperature of between 450 and 800 DEG C, at a pressure of between 0.1 and 3 Atm absolute and with a GHSV space velocity of between 100 and 10000 h<-1>, said paraffins with a catalytic system containing chromium oxide, tin oxide, at least one alkaline metal oxide(M)and an alumina carrier, in delta or theta phase or in mixed delta and theta or theta and alpha or delta, theta and alpha phases, modified with silica, in which: the chromium, expressed as Cr2O3, is in a quantity of between 6 and 30% by weight; the tin, expressed as SnO, is in a quantity of between 0.1 and 3.5% by weight; the alkaline metal, expressed as M2O, is in a quantity of between 0.4 and 3% by weight; the silica is in a quantity of between 0.08 and 3% by weight, the complement to 100 being alumina, b)in regenerating said catalytic system in a regenerator by burning the coke deposited on its surface operating at a temperature of more than 400 DEG C.
Description
The present invention relates to by corresponding paraffins, particularly C
2-C
20(paraffinic hydrocarbons with 2-20 carbon atom) paraffin dehydrogenation obtains the method for light olefin.
Alkene is the important intermediate of preparation chemical various in style, and these chemical have, for example polypropylene, uprising additive (MTBE), superoctane fuel, alkyl derivative and many other products.
Although the demand to these derivatives increases day by day, their industrial production process usually is subjected to the restriction of limited existing alkene.For example, in preparation MTBE, be subjected to the restriction of iso-butylene.
So just make us will find other sources that alkene is supplied with, and traditional source (FCC, cracker), in these sources that become more and more important, it is the dehydrogenation reaction of light paraffins that a representative is arranged.Though from stoichiometric viewpoint is simple, it exists some problems about thermodynamics and kinetics.This reaction is thermo-negative reaction, therefore will be subjected to the restriction of thermodynamic(al)equilibrium; So just cause for dehydrogenation C
2-C
4The paraffinic hydrocarbons temperature must be higher than 500 ℃, and at every turn by having economic acceptable transformation efficiency.In addition, because therefore the endothermic nature of reaction is necessary to provide the system with heating.
Although use high service temperature, the dehydrogenation rate remains low, therefore is necessary to operate in the presence of appropriate catalyst.This catalyzer must be heat-staple, and can guarantee the highly selective to required alkene, makes isomerization, cracking, coking and aromizing side reaction minimum and guarantee industrial effective conversion value.
The inevitable coke that forms makes catalytic activity reduce gradually on the catalyzer, therefore must carry out regular regeneration.
Therefore the prescription catalyzer must have high stability under reaction that is stood and regeneration condition.
Carry out some effort and found the catalytic composition of the requirement that can satisfy these class methods.
In fact patent documentation has listed several catalytic compositions, and these catalytic compositions have used precious metal and combined other chemical substances (US3531543; US4786625; US4886928; EP351067), and in the presence of promotor, also use metal oxide, comprise the Cr on the carrier as a rule
2O
3(US2945823; US2956030; US2991255; GB2162082).
Yet these two kinds of catalyst formulations all have shortcoming: those catalyzer that used precious metal need special dehydrogenation activity of handling (US4438288) with the protection metallics at regeneration period, for example, use the muriate aftertreatment, reduce processing subsequently; Those are based on the chromium oxide catalyst that is loaded on aluminum oxide, silicon oxide, the silica-alumina etc., it is characterized in that they have low selectivity to alkene, this is because their acid matter, this acidity matter can cause addition reaction such as isomerization, cracking, coking and aromatization, and these reactions generally are acid catalyzed reactions.
Can improve selectivity by adding basic metal and/or alkaline earth metal oxide modified catalyst prescription to alleviate acid matter to alkene.
Document discloses (J.Phys.Chem., Vol.66,1962) add the catalytic performance that a large amount of basic oxide can endanger prescription in order to improve selectivity, this is owing to the strong interaction with chromic oxide has suppressed dehydrogenation activity, stablize owing to adding a large amount of alkaline substance simultaneously, and make have be higher than+residual chromium of 3 oxidation state can not reduce fully, thereby reduced the selectivity of required alkene.
We are surprised to find that, by using special catalyst system, the selectivity of required alkene have obviously been improved, and this catalyst system mainly contains the Cr that is loaded in on the silica modified aluminum oxide
2O
3, and add stannic oxide.
Add tin and reduced forming of the product that generates by the acid catalysis side reaction widely, and olefine selective is had favorable influence.
The purpose of this invention is to provide the method that obtains light olefin by dehydrogenation of corresponding paraffins, this method comprises:
A) be 450-800 ℃ in temperature, pressure is the 0.1-3 bar absolute pressure, and the GHSV air speed is 100-10000 hour
-1Operational condition under, in paraffinic hydrocarbons described in the reactor and catalyst system reaction, this catalyst system contains chromic oxide, stannic oxide, at least a alkalimetal oxide (M) and alumina supporter, this alumina supporter is δ or θ phase or blended δ+θ or θ+α or δ+θ+α phase, and with silica modified, wherein:
-chromium is expressed as Cr
2O
3, its content is 6-30% (weight), preferred 13-25%;
-Xi is expressed as SnO, and its content is 0.1-3.5% (weight), preferred 0.2-2.8%;
-basic metal is expressed as M
2O, its content are 0.4-3% (weight), preferred 0.5-2.5%;
The content of-silicon oxide is 0.08-3% (weight),
Supply 100 with aluminum oxide,
B) in revivifier by burnt deposit at the lip-deep carbon deposit of the catalyst system described catalyst system of regenerating, service temperature is higher than 400 ℃.
Use basic metal, preferred potassium alleviates the acid matter of catalyst formulation to reduce less important reaction, the reaction of for example cracking, coking, aromizing and skeletal isomerization and key.
About carrier surface area, preferably it is less than 150 meters
2/ gram is measured with the BET method.
The method for preparing above-mentioned catalyst system mainly comprises chromium, basic metal and tin compound is dispersed on the carrier, this carrier comprise aluminum oxide (with δ or θ mutually or blended δ+θ or θ+α or δ+θ+α phase) and silicon oxide.
Be that some are dispersed in the method on the carrier with chromium, potassium and tin-oxide (Bivalent Tin and/or tetravalent tin) below, should understand the present invention and be not limited to these methods.
This dispersion treatment comprises: with the described carrier of solution impregnation that contains chromium, potassium and tin-oxide precursor, and then dry and calcining, perhaps ionic adsorption, separating liquid, drying and calcining solid then.In aforesaid method, preferred pickling process is according to " beginning wetting " method, with the solution impregnating carrier that contains all active ingredient precursors.
About tin, provided the additive method that it can be joined on the catalyst system:
-before dispersion chromium and potassium oxide precursor, tin is joined on the carrier;
-use the solution-treated that contains tin compound to contain the solid of chromium and potassium oxide compound by ion-exchange, impregnating method;
-before adding chromium and potassium oxide precursor, use and want the volatile compound of deposition substance tin to be deposited on the carrier by vapour deposition;
-use and want the volatile compound of deposition substance tin to be deposited on the solid that contains aluminum oxide, chromic oxide and potassium oxide by vapour deposition.
In aforesaid method, preferable methods is to use the solution of the precursor that contains chromium, potassium and tin-oxide active ingredient to be total to impregnated carrier, and vapour deposition tin.
Inorganic and the organic salt of tin, or Organometallic derivatives all can be used as the precursor of tin protoxide and/or stannic oxide.
Be subjected to by control can use not diffluent inorganic or organic salt in water after the pH of the solution that its solubleness influences.
According to aforesaid method, adopt the organic solvent of solubilized Organometallic derivatives, Organometallic derivatives is added in the catalyst system.
In air and/or oxygen, regenerate, for example can improve the temperature of catalyst system self to suitable value by the suitable fuel that burns.After this regenerative response, the reduction that must carry out catalyzer is with the 6 valency chromium of reduction in regeneration period formation.
Described method is applicable to any De-hydrogen Technology, no matter it is fixed bed, fluidized-bed or thermopnore.
This method is preferably carried out in fluidised bed system, and this system mainly comprises reactor and revivifier, and dehydrogenation reaction takes place in reactor, passes through the during reaction sedimentary coke regenerated catalyst of burning in revivifier.
In the reactor-regenerator system, catalyzer is with the circulation continuously between reactor and revivifier of its fluidized, this make this method operate continuously and by regenerated catalyst provide the reaction necessary heat, regenerated catalyst is to enter reactor with the temperature that is higher than average reaction temperature.Make catalyzer keep fluidized in reactor by reaction gas, reaction gas is to enter catalyst bed by specific system of distribution from the bottom.
The gas that reacted is by leaving reactor from top after cyclone system or other fines separation systems that is fit to; Then this gas can be sent into heat exchanger with preheated feed, send into segregation section then, reclaim the alkene that produces at segregation section, and unreacted paraffins be capable of circulation to synthesis step, isolating by product also can be used as the fuel gas in the revivifier.
When there is the esterification device in the downstream in dehydrogenation, only eliminate by product with segregation section.
In reactor, be in the catalyzer and the gas phase counter-current flow of fluidized, catalyzer enters catalyst bed from top by sparger, this sparger is evenly distributed in bed face with catalyzer, and leave reactor from the bottom, enter desorption zone by gravity, this desorption zone is the part of reactor, its diameter is less than or equal to reaction zone, in desorption zone, interparticle gas is replaced and desorb, so that the gas of replacement or desorb enters reaction zone again to avoid the loss of reactant or product by nitrogen or the methane of introducing from the bottom.
The catalyzer that will still be in fluidized by pressurized air is sent into revivifier then.
In fluidized-bed reactor, preferably under following condition, operate:
-by control temperature is remained between 450-650 ℃ to the regenerated catalyst flow velocity, this depends on paraffinic hydrocarbons to be processed or alkane mixture;
-pressure is normal atmosphere or a little higher than normal atmosphere;
-air speed is 100-1000 hour
-1(per hour the gas with every liter of catalyzer rises number), more preferably 150-200;
-residence time of catalyzer is 5-30 minute in fluidized-bed, preferred 10-15 minute is 0.2-10 minute in desorption zone.
Can be 10-90% with useful area, the net of preferred 20-40% flatly be installed in the inside of reactor, and the phase mutual edge distance of these nets is 20-200 centimetre.
The purposes of these nets is to prevent gas and solid remix, so that look like plug flow in the inside reactor gas flow, in this manner the transformation efficiency of paraffinic hydrocarbons and be maximum to the selectivity of required alkene.
Particularly selectivity is further maximized by axial heat distribution type, this axial heat distribution type is set up along bed, the local temperature that enters at the top of bed regenerated catalyst is the highest, and is minimum in the temperature of lower of bed, is preferably 15-65 ℃ along the temperature difference of bed.
In order to optimize axial heat distribution type, also can be in catalytic bed altitude distribution regenerated catalyst to change.Pneumatic conveyor system from the reactor to the revivifier comprises a line of pipes, this line of pipes has at least 1 district, catalyzer moves down in 1 district, preferably this district is remained under the intermediate conditions between minimum fluidisation and the minimum bubble formation by the gas that enters suitable amount at suitable height, in another district, catalyzer is moved up up to the top that reaches the revivifier catalytic bed, reduced the density of emulsion (emulsion) so significantly by enter gas in the bottom.
The gravel size decision of revivifier is similar to the size of reactor.
The suitable sparger catalyzer of autoreactor in the future is dispersed on the surface of catalytic bed.Regenerate in bed inside by the carbon deposit on the combustioncatalysts, and be higher than heatable catalyst under the average reactor temperature by methane or fuel gas and air or oxygen or the burning of other fuel gas.
Before sending into reactor, need under 650-680 ℃ of temperature reduction to handle regenerated catalyst 0.2-10 minute, then desorb burning and reductive product to eliminate 6 valency chromium.
Gas and solids back flow in revivifier, and air admission is to the bottom of catalytic bed, and fuel gas is suitably highly entering along bed.
Leave revivifier and contain nitrogen and cyclonic separator that the gas of products of combustion can be by being positioned at device top or other system to isolate the accumulative powder, gas is sent into heat exchanger with the preheated burning air after then leaving revivifier.
Before entering atmosphere, gas can be by filtering system or other equipment to reduce content of powder to tens milligrams of powder of every standard cubic meter gas.
Owing to carry out catalyticcombustion being lower than under 700 ℃ of temperature, the content of carbon monoxide and oxynitride is such so that does not need to be further purified processing in discharging gas.
In revivifier, preferably operate under following condition: pressure is normal atmosphere or a little higher than normal atmosphere, and air speed is 100-1000 hour
-1, the solid residence time is 5-60 minute, more preferably 20-40 minute.
Regenerated catalyst is transported to reactor to be transported to the identical mode of revivifier with spent catalyst.
She Ji reactor-regenerator system makes device constant in operating parameters and the property retention of whole technique operating period like this.
Regular discharge section catalyzer and replace from system, but operation that needn't interrupting device with the live catalyst of equivalent.
Use the advantage of fluidized-bed reactor-regenerator system to be summarized as follows:
Best temperature distribution makes the productive rate maximum of alkene in the-reactor;
-directly be sent to reactor by the regenerated catalyst heat: do not have the strong remix of heat exchange surface and fluidized-bed, prevented to reduce the optionally formation of high-temperature point;
-bed process does not need hydrogen recycle, sees that from the thermodynamics viewpoint hydrogen recycle is deleterious, but is necessary for the retentive control temperature in other configurations;
-other all operations all can be carried out continuously, and do not need the retouching operation parameter in the time limit in the entire operation of device;
-have very big handiness according to operation with respect to the existing production capacity device of designed capacity;
-in the district that separates naturally, react and regenerate, and hydrocarbon stream and oxygenate stream are without any mixing;
-operation is to carry out under normal atmosphere or high slightly pressure, therefore can not have air to infiltrate reaction zone from the outside;
-needn't special processing reduce the discharging of gas pollutant.
Fig. 1 has shown can applicable above-mentioned reactor-regenerator schema.
Hydrocarbon charging (1) enters reactor (A) by the sparger (not drawing among the figure) that is fit to, and gas leaves reactor from pipeline (4) after by cyclonic separator FA after the reaction.
Regenerated catalyst (5) arrives the top of catalytic bed and leaves reactor (A) and leads to desorption tower (B), and catalyzer contacts with stripping gas (2) in desorption tower.Enter transfer lime (6) with rear catalyst, catalyzer is admitted to revivifier (D) in transfer lime, is the top of sending into catalytic bed strictly speaking.
In this case, the single pipeline table that enters gas along line of pipes is shown (6).Line of pipes is characterised in that it is that U-shaped is connected to the lower section with between top in this uses.Catalyzer is descending along revivifier (D), enters reducer, enters desorption tower (G) then, enters line of pipes (C) at last and sends into reactor.Enter regeneration air (8) by the sparger (not drawing among the figure) that is fit to again, burning gas (9) and stripping gas (10), burning gas (9) is identical with the gas that is used for (E) reducing catalyst.
Gas by cyclonic separator FD after (7) leave.
Several embodiment are provided below, should think that these embodiment are limitations of the present invention.
Embodiment 1 (Comparative Examples)
Prepare the microspheroidal pseudobochmite by spraying drying hydrated aluminum oxide colloidal sol and Ludox silicon oxide, wherein having added (1.2% (weight)) particle diameter is the silicon oxide of 5-300 micron.
The pseudobochmite sample is heat-treated, be included in 450 ℃ and calcined 1 hour for the first time down, then in dry air stream, under 1030 ℃, calcined again 4 hours.
The specific surface of the product that obtains is 100 meters
2/ gram, porosity are 0.34 cubic centimetre/gram, mainly comprise δ and θ transitional alumina, also contain a spot of αYang Hualv (seeing the XRD spectrum of Fig. 2).
Use incipient wetness method in deionized water, to contain 67.5 gram CrO with 68 cubic centimetres that remain under 85 ℃
3Aqueous solution dipping 200 these aluminum oxide of gram of (99.8% (weight)) and 6.4 gram KOH (90% (weight)).Impregnation product was at room temperature placed 1 hour, and is following dry 15 hours at 90 ℃ then.The final drying product activates 4 hours down at 750 ℃ in dry air stream.
The weight that detects catalyst formulation is composed as follows: 20%Cr
2O
3, 1.89%K
2O, 1.25%SiO
2, Al
2O
3Be supplemented to 100.
Under 540-580 ℃ of temperature, be determined at catalytic performance in the dehydrogenation of isobutane reaction with the method for having narrated, the results are shown in table 1.
In deionized water, contain 68.3 with down 68 cubic centimetres of embodiment 1 uniform temp and restrain CrO with remaining on according to the method described above
3(99.8% (weight)) and 6.48 gram KOH (90% (weight)) and 4.13 gram SnC
2O
4Aqueous solution dipping 200 grams of (99.9% (weight)) are according to the micro-ball gamma aluminum oxide of embodiment 1 described method preparation.
Handle impregnation product according to the described method of the foregoing description and obtain catalyzer, it is as follows that the weight of this catalyzer is formed detection: 20%Cr
2O
3, 1.89%K
2O, 0.9%SnO, 1.23%SiO
2, Al
2O
3Be supplemented to 100.
Catalytic performance in the dehydrogenation of isobutane reaction is shown in the table 1.
Embodiment 3
In deionized water, contain 68.8 with down 68 cubic centimetres of embodiment 1 uniform temp and restrain CrO with remaining on according to the method described above
3(99.8% (weight)) and 6.52 gram KOH (90% (weight)) and 5.61 gram SnC
2O
4Aqueous solution dipping 200 grams of (99.9% (weight)) are according to the micro-ball gamma aluminum oxide of embodiment 1 described method preparation.
Handle impregnation product according to the described method of the foregoing description and obtain catalyzer, this catalyzer has following weight and forms: 20%Cr
2O
3, 1.89%K
2O, 1.4%SnO, 1.22%SiO
2, Al
2O
3Be supplemented to 100.
Catalytic performance in the dehydrogenation of isobutane reaction is shown in the table 1.
In deionized water, contain 67.9 with down 68 cubic centimetres of embodiment 1 uniform temp and restrain CrO with remaining on according to the method described above
3(99.8% (weight)), 6.44 gram KOH (90% (weight)) and 1.78 gram SnC
2O
4Aqueous solution dipping 200 grams of (99.9% (weight)) are according to the micro-ball gamma aluminum oxide of embodiment 1 described method preparation.
Handle impregnation product according to the described method of the foregoing description and obtain catalyzer, this catalyzer has following weight and forms: 20%Cr
2O
3, 1.89%K
2O, 0.45%SnO, 1.22%SiO
2, Al
2O
3Be supplemented to 100.
Catalytic performance in the dehydrogenation of isobutane reaction is shown in the table 1.
In deionized water, contain 67.7 with down 68 cubic centimetres of embodiment 1 uniform temp and restrain CrO with remaining on according to the method described above
3(99.8% (weight)) and 6.42 gram KOH (90% (weight)) and 0.91 gram SnC
2O
4Aqueous solution dipping 200 grams of (99.9% (weight)) are according to the micro-ball gamma aluminum oxide of embodiment 1 described method preparation.
Handle impregnation product according to the described method of the foregoing description and obtain catalyzer, this catalyzer has following weight and forms: 20%Cr
2O
3, 1.89%K
2O, 0.23%SnO, 1.25%SiO
2, Al
2O
3Be supplemented to 100.
Catalytic performance in the dehydrogenation of isobutane reaction is shown in the table 1.
Use incipient wetness method in nitrogen divides, to contain 3.99 gram dissolved dimethoxy dibutyl tin (CH with 44 cubic centimetres
3O)
2(Sn (C
4H
9)
2Methanol solution dipping 200 grams according to the micro-ball gamma aluminum oxides of embodiment 1 described method preparation.Impregnation product was at room temperature placed 1 hour, and is dry down up to removing methyl alcohol fully at 90 ℃ then.
The final drying product was calcined 4 hours down at 750 ℃ in dry air atmosphere.
The weight that detects catalyst formulation is composed as follows: 20%Cr
2O
3, 1.89%K
2O, 0.87%SnO, 1.23%SiO
2, Al
2O
3Be supplemented to 100.
Catalytic performance at the dehydrogenation of isobutane reacting middle catalyst is shown in table 1.
Use vapor deposition techniques to restrain and embodiment 6 used identical catalyzer with tin modification 200.For this reason, with the catalyst sample quartz reactor of packing into, the ceramic sparger that this reactor is equipped with the thermometer folder and has a calibration porosity is to obtain the uniform distribution of bed bottom nitrogen.The reactor that will have these materials is put into the electric furnace with local heating, adds nitrogen (40-45 mark rise/hour) to keep the fluidisation of material by the porous sparger.When reaching 200 ℃ of preset temperatures that are used for the tin deposit, before adding the tin precursor, carry out the axial heat distribution of bed.
In case assert bed temperature preset temperature ± when being even in 1 ℃ of scope, under 150-170 ℃ of temperature, the 10-15 mark is risen/hour with dimethoxy dibutyl tin (CH
3O)
2(Sn (C
4H
9)
2Saturated nitrogen is incorporated into catalytic bed.Saturated logistics enters catalytic bed and porous sparger, and mixes with fluidisation nitrogen in the downstream of dividing plate from being the top adding of the reactor of silica tube fully.The logistics that reactor is left in cooling reclaims unreacted dimethoxy dibutyl tin.
Determine the charging capacity of tin by the weight that detects the residual precursor in the saturator.
When obtaining the theoretical precursor that carries the aequum of tin amount and be removed, interrupt operation.
The temperature of rising catalytic bed is up to reaching 750 ℃, and keeps 4 hours to carry out the activation of material.It is composed as follows that analyzing activated product determines its weight: 20%Cr
2O
3, 1.89%K
2O, 0.33%SnO, 1.24%SiO
2, Al
2O
3Be supplemented to 100.
The catalytic performance of prescription catalyzer is shown in table 1 in the dehydrogenation of isobutane reaction.
Embodiment 8 (Comparative Examples)
1000 grams are heat-treated according to the pseudobochmite sample of embodiment 1 described method preparation, be included in 450 ℃ and calcined 1 hour for the first time down, then in dry air stream, under 1000 ℃, calcined again 4 hours.The surface-area of calcinate is 130 meters
2/ gram, porosity are 0.49 cubic centimetre/gram, and comprise δ and θ transitional alumina (seeing the XRD spectrum of Fig. 3).
Use incipient wetness method, keep the temperature identical to contain 66.8 and restrain CrO with 74 cubic centimetres with embodiment 1
3Aqueous solution dipping 150 these aluminum oxide of gram of (99.8% (weight)) and 5.36 gram salt of wormwood (45%w/wKOH).Impregnation product was at room temperature placed 1 hour, and is following dry 15 hours at 90 ℃ then.The final drying product activates 4 hours down at 750 ℃ in dry air stream.The weight that detects catalyst formulation is composed as follows:
25%Cr
2O
3, 1%K
2O, 1.18%SiO
2, Al
2O
3Be supplemented to 100.Measuring this prescription catalyzer under the 560-600 ℃ of temperature in the dehydrogenating propane reaction, the performance that obtains is shown in table 1.
Adopt incipient wetness method, contain 3.75 gram dimethoxy dibutyl tin (CH with 74 cubic centimetres
3O)
2Sn (C
4H
9)
2The identical aluminum oxide of methanol solution dipping 150 grams and embodiment 8.
Impregnation product was placed 1 hour, dry up to removing methyl alcohol fully down at 90 ℃ then.At last desciccate was calcined 2 hours down at 600 ℃ in dry air stream.According to embodiment 8 described methods, under the temperature identical, contain 67.6 gram CrO with 74 cubic centimetres with embodiment 1
3The aqueous solution dipping incinerating product of (99.8% (weight)) and 5.42 gram salt of wormwood (45%w/wKOH) obtains having the catalyzer that following weight is formed: 25%Cr
2O
3, 1%K
2O, 0.84%SnO, 1.18%SiO
2, Al
2O
3Be supplemented to 100.Catalytic performance in the dehydrogenating propane reaction is shown in table 2.
Embodiment 10
Adopt and embodiment 9 described same procedure, contain 7.63 gram dimethoxy dibutyl tin (CH with 74 cubic centimetres
3O)
2Sn (C
4H
9)
2The methanol solution dipping 150 grams aluminum oxide identical with being used for embodiment 9.According to embodiment 8 described same procedure, under the condition identical, under the temperature identical, contain 68.4 gram CrO with 74 cubic centimetres with embodiment 1 with embodiment 9
3The aqueous solution dipping incinerating product of (99.8% (weight)) and 5.48 gram salt of wormwood (45%w/wKOH) obtains having the catalyzer that following weight is formed: 25%Cr
2O
3, 1%K
2O, 1.68%SnO, 1.17%SiO
2, Al
2O
3Be supplemented to 100.Measure the prescription catalyzer in the dehydrogenating propane reaction, the performance that obtains is shown in table 2.
Embodiment 11
Adopt and embodiment 9 described same procedure, contain 11.61 dimethoxy dibutyl tin (CH with 74 cubic centimetres
3O)
2Sn (C
4H
9)
2The methanol solution dipping 150 grams aluminum oxide identical with being used for embodiment 9.According to embodiment 8 described same procedure, under the condition identical, under the temperature identical, contain 69.2 gram CrO with 74 cubic centimetres with embodiment 1 with embodiment 9
3The aqueous solution dipping incinerating product of (99.8% (weight)) and 5.55 gram salt of wormwood (45%w/wKOH) obtains having the catalyzer that following weight is formed: 25%Cr
2O
3, 1%K
2O, 2.52%SnO, 1.14%SiO
2, Al
2O
3Be supplemented to 100.The catalytic performance of prescription catalyzer is shown in table 2 in the dehydrogenating propane reaction.
Embodiment 12
Under the temperature identical with embodiment 1, with 74 cubic centimetres of aqueous solution dipping 150 grams aluminum oxide identical with being used for embodiment 8, be dissolved with following compounds in this aqueous solution: 68.4 restrain CrO
3(99.8% (weight)) and 5.49 gram salt of wormwood (45%w/wKOH) and 5.35 gram SnC
2O
4(99.9%w/w).Use the method identical to carry out drying and activation with embodiment 1.The weight that determines the prescription catalyzer is composed as follows: 25%Cr
2O
3, 1%K
2O, 1.68%SnO, Al
2O
3Be supplemented to 100.Catalytic performance in the dehydrogenating propane reaction is shown in table 2.
Embodiment 13
According to embodiment 6 described methods, contain 3.03 gram (CH with 39 cubic centimetres
3O)
2Sn (C
4H
9)
2Methanol solution dipping 150 grams with the catalyzer of embodiment 8 described methods preparations.The activation post analysis is measured the composition of catalyzer and is detected in the dehydrogenating propane reaction.
The weight that determines is composed as follows: 24.8%Cr
2O
3, 0.99%K
2O, 0.91%SnO, 1.17%SiO
2, Al
2O
3Be supplemented to 100.Catalytic performance is listed in table 2.
Embodiment 14
Adopt embodiment 2 described methods, contain 37.2 gram CrO with 68 cubic centimetres that remain under 85 ℃ of temperature
3(99.8% (weight)), 5.87 gram KOH (90% weight) and 3.26 gram SnC
2O
4(99.9%) aqueous solution dipping 200 restrains identical aluminum oxide used in identical embodiment, preparation 235 gram catalyzer, and this catalyzer has following weight and forms: 12%Cr
2O
3, 1.36%SiO
2, 1.89%K
2O, 0.9%SnO, Al
2O
3Be supplemented to 100.
Measure catalyzer in the dehydrogenation of isobutane reaction, the performance that obtains is shown in table 1.
Embodiment 15
The pseudobochmite sample that obtains according to embodiment 1 method by calcining, but non-oxidation silicon in the sample, obtaining specific surface is 104 meters
2/ gram and porosity are 200 gram aluminum oxide of 0.34 cubic centimetre/gram, contain 68.3 gram CrO with 68 cubic centimetres
3(99.8% (weight)), 6.48 gram KOH (90% weight) and 4.13 gram SnC
2O
4(99.9%) the aqueous solution floods this aluminum oxide, and the catalyzer that obtains has following weight and forms: 20%Cr
2O
3, 1.89%K
2O, 0.9%SnO, Al
2O
3Be supplemented to 100.Measure catalyst formulation in the dehydrogenation of isobutane reaction, the performance that obtains is listed in table 1.
Embodiment 16
Prepare catalyst sample with method and the aluminum oxide identical with embodiment 2, this catalyzer has following weight and forms: 20%Cr
2O
3, 3%K
2O, 0.9%SnO, 1.22%SiO
2, Al
2O
3Be supplemented to 100.Catalytic performance in the dehydrogenation of isobutane reaction is listed in table 1.
Embodiment 17
Prepare catalyst sample with method and the aluminum oxide identical with embodiment 2, this catalyzer has following weight and forms: 20%Cr
2O
3, 0.2%K
2O, 0.9%SnO, 1.27%SiO
2, Al
2O
3Be supplemented to 100.Catalytic performance in the dehydrogenation of isobutane reaction is listed in table 1.
The catalysis experiment
The quartz reactor that the sparger with calibration porosity has been installed in use is determined at the product for preparing among the embodiment 1-17 in fluidized-bed, this sparger is also made by quartz.Head at reactor is equipped with expander, and its effect is to slow down effluent to make fine particle fall back catalytic bed.The characteristic of catalytic cycle simulation industrial reactor, this catalytic cycle comprises: a step of reaction, wherein add hydrocarbon, carried out 15 minutes, in a stripping stage, wherein in 10 minutes, feed nitrogen catalyzer is separated with the product of absorption, a regeneration stage, wherein add in test the regeneration gas that contains air, this test was carried out 30 minutes, the washing stage with nitrogen, carried out at least 10 minutes, a reduction phase, wherein feed the reducing gas that contains methane, carry out 4 minutes to reduce the 6 valency chromium that in the regeneration stage, form, a washing stage with nitrogen, carried out at least 10 minutes, then step of reaction was carried out 15 minutes.It is to carry out being higher than under the temperature of temperature of reaction that the prerequisite of industrial fluidized bed method of dehydrogenating proposes regeneration, regeneration and reduction are to carry out under 650 ℃ in catalytic test, and under the situation of dehydrogenating propane the reaction be under 560-600 ℃ of temperature, to carry out, under the situation of dehydrogenation of isobutane the reaction be under 540-580 ℃ of temperature, to carry out.
The air speed of reactant is 400 ± mark liter/catalyzer. hour.In first catalytic test, before carrying out dehydrogenation reaction, reduce all catalyzer according to the method for having described.
The reactant of sending into reactor feeds intake by weight.
Reaction and the reactor effluent in stripping stage first by cold-trap to stop heavy product, measure weight %, carbon % and the hydrogen % of this product then, be collected in then in the multilayer sample sack, this sample sack does not have avidity to hydro carbons.Then with the capacity of metering volumetric pump working sample bag and use gas chromatographic analysis.
Use N at last
2Behind the stripping 10 minutes, take out catalyst sample, measure the amount of coke that forms.With the data that obtain like this input computer to calculate material balance, transformation efficiency and to various product selectivity.
Table 1
Dehydrogenation of isobutane
GH-SV=(400+-5) mark rises different-C4H10/h/l catalyzer
Fluidized-bed
Embodiment C r
2O
3K
2O SiO
2SnO temperature inversion rate selectivity yield
W/w% ℃ of w/w% w/w% w/w% (%-is different-(%mol. (%mol.
C4H10) different-different-
C
4H
8) C
4H
8)
1 contrast 20 1.89 1.25 does not have 560 54 88 47.5
2 20 1.89 1.23 0.90 570 54 94 50.7
3 20 1.89 1.22 1.40 589 54 92 49.7
4 20 1.89 1.25 0.45 565 54 91 49.1
5 20 1.89 1.25 0.23 562 54 90 48.6
6 20 1.89 1.23 0.87 575 54 92 49.7
7 20 1.89 1.24 0.33 564 54 91 49.1
14 12 1.89 1.36 0.90 573 54 90 48.6
15 contrasts 20 1.89 do not have 0.90 568 54 89 48.1
16 20 3.0 1.22 0.9 570 54 87 46.9
17 20 0.20 1.27 0.9 568 54 70 37.8
Table 2
Dehydrogenating propane
GHSH=(400+-5) Nl/h/l catalyzer
Fluidized-bed
Embodiment C r
2O
3K
2O SiO
2SnO temperature inversion rate selectivity yield
w/w％ w/w％ w/w％ w/w％ ℃ (％- (％mol. (％mol.
C
3H
8) C
3H
6) C
3H
6)
8 contrasts 25 1.0 1.18 do not have 566 37 78 28.9
9 25 1.0 1.18 0.84 570 37 86 31.8
10 25 1.0 1.17 1.68 580 37 88 32.5
11 25 1.0 1.14 2.52 588 37 84 31.1
12 25 1.0 1.15 1.68 582 37 87 32.2
13 24.8 0.99 1.17 0.91 590 37 89 32.9
Claims (8)
1. one kind obtains the method for light olefin by dehydrogenation of corresponding paraffins, comprising:
A) be 450-800 ℃ in temperature, pressure is the 0.1-3 bar absolute pressure, and the GHSV air speed is 100-10000 hour
-1Operational condition under, in the reaction of the paraffinic hydrocarbons described in the reactor and catalyst system, this catalyst system contains chromic oxide, stannic oxide, at least a alkalimetal oxide M
2O and alumina supporter, this alumina supporter are δ or θ phase or blended δ+θ or θ+α or δ+θ+α phase, and with silica modified, wherein:
-chromium is expressed as Cr
2O
3, its content is 6-30% weight;
-Xi is expressed as SnO, and its content is 0.1-3.5% weight;
-basic metal is expressed as M
2O, its content are 0.4-3% weight;
The content of-silicon oxide is 0.08-3% weight,
Supply 100 with aluminum oxide,
B) in revivifier by the lip-deep carbon deposit of the combustion catalysis system described catalyst system of regenerating, service temperature is higher than 400 ℃.
2. according to the process of claim 1 wherein:
-chromium is expressed as Cr
2O
3, its content is 13-25% weight;
-Xi is expressed as SnO, and its content is 0.2-2.8% weight;
-basic metal is expressed as M
2O, its content are 0.5-2.5% weight.
3. according to the process of claim 1 wherein that basic metal is potassium.
4. according to the process of claim 1 wherein that the surface-area of carrier is less than 150 meters
2/ gram.
5. according to the process of claim 1 wherein that reactor and revivifier are fluidized bed types.
6. according to the method for claim 5, dehydrogenation is to carry out under following condition: temperature is 450-650 ℃, and pressure is normal atmosphere or a little higher than normal atmosphere, and the GHSV air speed is 100-1000 hour
-1, the residence time of catalyzer in fluidized-bed is 5-30 minute.
7. according to the method for claim 6, wherein air speed is 150-200 hour
-1, the residence time of catalyzer is 10-15 minute.
8. according to the method for claim 5, wherein regeneration is to use air or oxygen or other burning carrier gas and carries out under following condition: temperature is higher than the medial temperature of reactor, and pressure is normal atmosphere or a little higher than normal atmosphere, and air speed is 100-1000 hour
-1, the residence time is 5-60 minute.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT01807A/97 | 1997-07-29 | ||
| IT97MI001807A IT1293497B1 (en) | 1997-07-29 | 1997-07-29 | PROCEDURE TO OBTAIN LIGHT OLEFINS BY DEHYDROGENATION OF THE CORRESPONDING PARAFFINS |
| IT01807A/1997 | 1997-07-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1213662A CN1213662A (en) | 1999-04-14 |
| CN1158229C true CN1158229C (en) | 2004-07-21 |
Family
ID=11377659
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB981178081A Expired - Fee Related CN1158229C (en) | 1997-07-29 | 1998-07-28 | Process for obtaining light olefins by dehydrogenation of corresponding paraffins |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US6362385B1 (en) |
| EP (1) | EP0894781B1 (en) |
| CN (1) | CN1158229C (en) |
| AR (1) | AR013373A1 (en) |
| CA (1) | CA2241226C (en) |
| DE (1) | DE69802475T2 (en) |
| DK (1) | DK0894781T3 (en) |
| DZ (1) | DZ2572A1 (en) |
| IT (1) | IT1293497B1 (en) |
| SA (1) | SA98190826B1 (en) |
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| US20070112159A1 (en) * | 2005-11-11 | 2007-05-17 | Heinz Boelt | Process for the production of polypropylene from propane |
| US8653317B2 (en) * | 2009-03-19 | 2014-02-18 | Dow Global Technologies Llc | Dehydrogenation process and catalyst |
| US8835347B2 (en) * | 2009-06-05 | 2014-09-16 | Basf Corporation | Alkane dehydrogenation catalysts |
| US8624074B2 (en) | 2010-03-22 | 2014-01-07 | Uop Llc | Reactor flowscheme for dehydrogenation of propane to propylene |
| WO2011159303A1 (en) * | 2010-06-17 | 2011-12-22 | Basf Corporation | Alkane dehydrogenation catalysts |
| US8603406B2 (en) | 2010-08-30 | 2013-12-10 | Uop Llc | For drying regenerated catalyst in route to a propane dehydrogenation reactor |
| US8513149B2 (en) | 2010-08-30 | 2013-08-20 | Uop Llc | Method for drying regenerated catalyst in route to a propane dehydrogenation reactor |
| US9150465B2 (en) * | 2010-09-21 | 2015-10-06 | Uop Llc | Integration of cyclic dehydrogenation process with FCC for dehydrogenation of refinery paraffins |
| US8927799B2 (en) * | 2010-11-01 | 2015-01-06 | Uop Llc | Propane dehydrogenation process utilizing fluidized catalyst system |
| US8895468B2 (en) | 2011-09-20 | 2014-11-25 | Basf Corporation | Chromia alumina catalysts for alkane dehydrogenation |
| EP2890496B1 (en) | 2012-08-28 | 2021-04-28 | Dow Global Technologies LLC | Catalyst composition and reactivation process useful for alkane dehydrogenations |
| EP2794091A4 (en) * | 2012-09-20 | 2015-09-23 | Basf Corp | Chroma alumina catalysts for alkane dehydrogenation |
| US9023285B2 (en) * | 2012-11-20 | 2015-05-05 | Uop Llc | Counter-current fluidized bed reactor for the dehydrogenation of olefins |
| JP6085206B2 (en) | 2013-03-26 | 2017-02-22 | 住友化学株式会社 | Method for producing methacrylate ester |
| US20160068454A1 (en) | 2013-04-08 | 2016-03-10 | Saudi Basic Industries Corporation | Reactor and process for paraffin dehydrogenation to olefins |
| RU2538960C1 (en) * | 2013-10-09 | 2015-01-10 | Открытое акционерное общество "Нижнекамскнефтехим" | Catalyst of dehydration of c4-c5 paraffin hydrocarbons |
| CN104043443B (en) * | 2014-06-13 | 2016-06-08 | 烟台大学 | A kind of high strength low-carbon alkane dehydrogenating catalyst and its preparation method |
| US10144680B2 (en) | 2014-10-20 | 2018-12-04 | China Petroleum & Chemical Corporation | Process for producing light olefins |
| CN105521790B (en) * | 2014-10-22 | 2017-11-24 | 中国石油化工股份有限公司 | A kind of preprocess method of catalyst for dehydrogenation of low-carbon paraffin |
| CN107206339B (en) * | 2015-02-27 | 2020-05-12 | 沙特基础工业全球技术有限公司 | Minimizing coke formation in a reactor stripper |
| RU2731380C2 (en) | 2015-03-30 | 2020-09-02 | Дау Глоубл Текнолоджиз Ллк | Integrated method of dehydration of c3-c4-hydrocarbons |
| AR111737A1 (en) * | 2017-05-05 | 2019-08-14 | Dow Global Technologies Llc | EXTRACTION SYSTEM OF BULK CATALYST AND METHODS FOR THE USE OF THE SAME |
| CN110831916A (en) * | 2017-05-25 | 2020-02-21 | 斯克利普斯研究所 | Direct oxidation of olefins to oxygenates |
| EP3845514A1 (en) * | 2020-01-02 | 2021-07-07 | Indian Oil Corporation Limited | A catalyst composition for oxidative dehydrogenation of alkane |
| CN116322962A (en) | 2020-07-28 | 2023-06-23 | 道达尔能源一技术 | Process for carrying out endothermic dehydrogenation and/or aromatization reactions in a fluidized bed reactor |
| WO2024059600A1 (en) * | 2022-09-14 | 2024-03-21 | Dow Global Technologies Llc | Methods for dehydrogenating hydrocarbons utilizing regenerators |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US2991255A (en) * | 1957-10-03 | 1961-07-04 | American Cyanamid Co | Extrusion of chromia alumina catalysts |
| US3692863A (en) * | 1968-10-22 | 1972-09-19 | Ashland Oil Inc | Dehydrogenation and dehydrocyclization method |
| US3647909A (en) * | 1970-02-10 | 1972-03-07 | Atlantic Richfield Co | Regeneration of chromia-alumina dehydrogenation catalyst |
| FR2197833A1 (en) * | 1972-08-30 | 1974-03-29 | Ashland Oil Inc | Dehydrogenation/dehydrocyclisation catalyst - contg group vib metals and tin or lead oxides |
| US4038215A (en) * | 1974-10-16 | 1977-07-26 | Petro-Tex Chemical Corporation | Dehydrogenation catalyst |
| FI852865L (en) * | 1984-07-25 | 1986-01-26 | Air Prod & Chem | FOERBAETTRAD KATALYSATOR FOER DEHYDRERING AV KOLVAETEN. |
| DE3841800A1 (en) * | 1988-12-12 | 1990-06-13 | Linde Ag | METHOD AND CATALYST FOR DEHYDRATING OR DEHYDROCYCLIZING HYDROCARBONS |
| IT1238085B (en) | 1990-02-07 | 1993-07-05 | Snam Progetti | CATALIC COMPOSITION FOR THE DEHYDROGENATION OF C2-C5 PARAFFINS |
| IT1254252B (en) | 1992-03-11 | 1995-09-14 | Snam Progetti | PROCEDURE FOR THE ACTIVATION OF CATALYTIC PRECURSORS FOR THE DEHYDROGENATION OF C2-C5 PARAFFINS AND CATALYTIC COMPOSITION ACTIVATED WITH SUCH PROCEDURE |
| IT1254988B (en) | 1992-06-23 | 1995-10-11 | Eniricerche Spa | Process for the dehydrogenation of light paraffins in a fluidised bed reactor |
| US5258567A (en) * | 1992-08-26 | 1993-11-02 | Exxon Research And Engineering Company | Dehydrogenation of hydrocarbons |
-
1997
- 1997-07-29 IT IT97MI001807A patent/IT1293497B1/en active IP Right Grant
-
1998
- 1998-07-16 EP EP98202399A patent/EP0894781B1/en not_active Expired - Lifetime
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Also Published As
| Publication number | Publication date |
|---|---|
| IT1293497B1 (en) | 1999-03-01 |
| EP0894781A1 (en) | 1999-02-03 |
| CA2241226A1 (en) | 1999-01-29 |
| AR013373A1 (en) | 2000-12-27 |
| DZ2572A1 (en) | 2003-02-22 |
| DE69802475D1 (en) | 2001-12-20 |
| CA2241226C (en) | 2008-02-12 |
| ITMI971807A1 (en) | 1999-01-29 |
| SA98190826B1 (en) | 2006-09-20 |
| EP0894781B1 (en) | 2001-11-14 |
| DK0894781T3 (en) | 2002-01-21 |
| CN1213662A (en) | 1999-04-14 |
| DE69802475T2 (en) | 2002-08-14 |
| US6362385B1 (en) | 2002-03-26 |
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